Adhesive resin laminate, laminate, and method of producing same

ABSTRACT

Provided are an adhesive resin laminate having an excellent adhesive force to two adherends, a laminate in which this adhesive resin laminate is laminated with two adherends, and a method of producing them. An adhesive resin laminate having at least a first adhesive layer and a second adhesive layer, in which the first adhesive layer includes a base resin and a crosslinking agent, the base resin is a modified polyolefin resin, the crosslinking agent is an epoxy-based compound, the second adhesive layer includes a polyolefin-based resin, and the first adhesive layer has a viscoelastic modulus measurement value E (150) at 150° C. of 1.0×10 4  Pa or more and 1.0×10 8  Pa or less.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Divisional of U.S. application Ser. No. 15/891,636filed Feb. 8, 2018, which claims priority from Japanese PatentApplication No. 2017-026762, filed Feb. 16, 2017. The entire teachingsof the above applications are incorporated herein by reference.

BACKGROUND OF THE INVENTION (1) Field of the Invention

The present invention relates to an adhesive resin laminate, a laminate,and a method of producing the same.

(2) Description of Related Art

Conventionally, as a material which adheres to an adherend such asmetal, a hot-melt adhesive having an acid-modified polyolefin resin hasbeen known.

For example, Japanese Unexamined Patent Application, First PublicationNo. 2012-001661 discloses an adhesive resin composition for a polyolefinmultilayered film containing a dibasic carboxylic acidanhydride-modified polyolefin resin having a weight average molecularweight of 15,000 to 150,000 and a solid content acid value of 100 to300, and a multilayer laminated film in which the adhesive resincomposition is laminated as an adhesive layer with another resin ormetal.

Japanese Unexamined Patent Application, First Publication No.2012-001661 describes that good adhesiveness to resin or metal or thelike can be obtained by using the relevant composition. Certainly, whenthe adhesive resin composition described in Japanese Unexamined PatentApplication, First Publication No. 2012-001661 is used, adhesion betweenan adhesive layer composed of the adhesive resin composition and anadherend can be improved, depending on the condition. However, when twoadherends composed of two different materials are adhered with theadhesive resin composition interposed therebetween, it is difficult tomatch the condition in order to realize good adhesiveness to bothadherends.

SUMMARY OF THE INVENTION

The present invention has been made in view of the above-mentionedcircumstances, and an object thereof is to provide an adhesive resinlaminate having an excellent adhesive force to two adherends, a laminatein which this adhesive resin laminate is laminated with two adherends,and a method of producing them.

In order to solve the above-mentioned problem, the present inventionprovides an adhesive resin laminate having at least a first adhesivelayer and a second adhesive layer, wherein the first adhesive layerincludes a base resin and a crosslinking agent, the base resin is amodified polyolefin resin, the crosslinking agent is an epoxy-basedcompound, the second adhesive layer includes a polyolefin-based resin,and the first adhesive layer has a viscoelastic modulus measurementvalue E (150) at 150° C. of 1.0×10⁴ Pa or more and 1.0×10⁸ Pa or less.

The epoxy-based compound contained in the first adhesive layer may be aphenol novolak-type epoxy resin.

The epoxy-based compound contained in the first adhesive layer mayinclude a bisphenol A skeleton.

The second adhesive layer may be a laminate of a plurality ofpolyolefin-based resin layers.

The second adhesive layer may include a layer including blockpolypropylene.

The second adhesive layer has a film thickness five times or more of afilm thickness of the first adhesive layer, and the second adhesivelayer may have a support property.

Also, the present invention provides a laminate including the adhesiveresin laminate and two adherends, the adhesive resin laminate and twoadherends being laminated in an order of a first adherend, the firstadhesive layer of the adhesive resin laminate, the second adhesive layerof the adhesive resin laminate, and a second adherend.

The first adherend may be metal, and the second adherend may be selectedfrom any one of a polyolefin resin, a polyamide resin, and a polyesterresin.

Also, the present invention provides a method of producing the adhesiveresin laminate, the method comprising (1) a step of dissolving themodified polyolefin resin and the epoxy-based compound in a solvent toproduce a coating liquid; (2) a step of coating the coating liquid on asubstrate film and drying the coating liquid to produce the firstadhesive layer; (3) a step of obtaining the second adhesive layer havinga film shape by extrusion molding; (4) a step of laminating the firstadhesive layer on the substrate film and the second adhesive layer; and(5) a step of peeling the substrate film to obtain the adhesive resinlaminate, in this order.

Also, the present invention provides a method of producing the laminate,the method comprising (1) a first step of laminating the first adherendand the first adhesive layer and heat-pressing the first adherend andthe first adhesive layer to laminate the first adherend and the adhesiveresin laminate; and (2) a step of laminating the second adherend and thesecond adhesive layer and heat-pressing the second adherend and thesecond adhesive layer at a temperature higher than a temperature in thefirst step by 30° C. or higher to laminate the second adherend and theadhesive resin laminate, in this order.

According to the present invention, there can be provided an adhesiveresin laminate having an excellent adhesive force to two adherends, alaminate in which this adhesive resin laminate is laminated with twoadherends, and a method of producing them.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a cross-sectional view schematically showing an adhesive resinlaminate of the present invention and two adherends; and

FIG. 2 is a graph exemplifying storage elastic modulus measurementresults of a first adhesive layer.

DETAILED DESCRIPTION OF THE INVENTION

The present invention will be illustrated below based on a preferredembodiment.

FIG. 1 schematically shows an adhesive resin laminate of the presentembodiment. An adhesive resin laminate 10 is a laminate having at leasta first adhesive layer 11 and a second adhesive layer 12. The firstadhesive layer 11 has a surface which can be in contact with a firstadherend 21. The second adhesive layer 12 has a surface which can be incontact with a second adherend 22.

The first adhesive layer 11 includes a base resin composed of a modifiedpolyolefin resin and a crosslinking agent which crosslinks the baseresin. In the first adhesive layer 11, a part or all of the base resinand a part or all of the crosslinking agent may have been reacted. Apart or all of the base resin and a part or all of the crosslinkingagent may have been unreacted. In the first adhesive layer 11, the baseresin may include a crosslinked resin in which the base resin has beencrosslinked with the crosslinking agent.

Examples of the modified polyolefin resin to be the base resin of thefirst adhesive layer 11 include one or two or more of an acid-modifiedpolyolefin resin, a hydroxy-modified polyolefin resin, a chlorinatedpolyolefin resin, and the like. Inter alia, from the viewpoint ofreactivity with an epoxy group, an acid-modified polyolefin resin whichhas been modified with unsaturated carboxylic acid or a derivativethereof is preferred.

Examples of a method of producing the acid-modified polyolefin resininclude a method of graft-modifying an unmodified polyolefin resin withan acid functional group-containing monomer by melting and kneadingthem, a method of copolymerizing an olefin monomer and an acidfunctional group-containing monomer, and the like. As the base resin ofthe first adhesive layer 11, the acid-modified polyolefin resin which isobtained by graft modification is preferred. It is preferable that graftmodification is performed in the presence of a radical polymerizationinitiator such as organic peroxide or an aliphatic azo compound.

In a constitution of the acid-modified polyolefin resin, examples of anolefin monomer when copolymerized with the acid functionalgroup-containing monomer, or an olefin monomer constituting theunmodified polyolefin resin include one or two or more of ethylene,propylene, 1-butene, isobutylene, 1-hexene, 1-octene, α-olefin, and thelike.

Examples of the unmodified polyolefin resin before graft modificationinclude one or two or more of polyethylene, polypropylene,poly-1-butene, polyisobutylene, a copolymer of ethylene and propylene, acopolymer of propylene and 1-butene, a random copolymer of propylene andethylene or α-olefin, a block copolymer of propylene and ethylene orα-olefin, and the like. Inter alia, a polypropylene-based resin such ashomopolypropylene which is a homopolymer of propylene, a block copolymerof propylene-ethylene, a random copolymer of propylene-ethylene or acopolymer of propylene-1-butene is preferred.

Molecular motion during heating of the first adhesive layer 11 ispromoted when a monomer constituting the acid-modified polyolefin resincontains 1-butene. When the base resin and the crosslinking agent havefunctional groups which can be reacted with each other, an opportunitythat the functional groups of the base resin and those of thecrosslinking agent are in contact with each other is increased, and as aresult, durability of the first adhesive layer 11 and adherence to anadherend are more improved.

The acid functional group-containing monomer is a compound having anethylenic double bond and an acid group or an acid anhydride group inthe same molecule. Examples of the acid group or the acid anhydridegroup to be an acid functional group include a carboxylic acid group(—COOH) and a carboxylic acid anhydride group (—CO—O—CO—). Examples of amonomer having the carboxylic acid group or the carboxylic acidanhydride group include one or two or more of unsaturated monocarboxylicacid, unsaturated dicarboxylic acid, unsaturated dicarboxylic acidanhydride, and the like.

In one or two or more of the acid-modified polyolefin resins, the sameacid functional group-containing monomer may be used, or different twoor more acid functional group-containing monomers may be used.

Examples of the unsaturated monocarboxylic acid include one or two ormore of α,β-unsaturated carboxylic acid monomers such as acrylic acid,methacrylic acid, crotonic acid, and isocrotonic acid.

Examples of the unsaturated dicarboxylic acid include one or two or moreof α,β-unsaturated dicarboxylic acids such as maleic acid, itaconicacid, citraconic acid, and fumaric acid, tetrahydrophthalic acid,methyltetrahydrophthalic acid, 5-norbornene-2,3-dicarboxylic acid (nadicacid), endo-bicyclo[2.2.1]-5-heptene-2,3-dicarboxylic acid (endic acid),and the like.

Examples of the unsaturated dicarboxylic acid anhydride include one ortwo or more of maleic acid anhydride, itaconic acid anhydride,citraconic acid anhydride, tetrahydrophthalic acid anhydride,methyltetrahydrophthalic acid anhydride, nadic acid anhydride, endicacid anhydride, and the like.

As the acid-modified polyolefin resin, due to high reactivity with anepoxy group contained in the crosslinking agent, an acid-modifiedpolyolefin resin having an acid anhydride group is preferred, anacid-modified polyolefin resin having a carboxylic acid anhydride groupis preferred, and a maleic acid anhydride-modified polyolefin resin isparticularly preferred. Inter alia, from the viewpoint of adhesivenessand a moderate melting point, a maleic acid anhydride-modifiedpolypropylene-based resin is preferred.

When the acid-modified polyolefin resin contains an unreacted acidfunctional group-containing monomer, an adhesive force may be reduced.For this reason, as the base resin of the first adhesive layer 11, anacid-modified polyolefin resin that does not include an unreacted acidfunctional group-containing monomer is preferred. An acid-modifiedpolyolefin resin from which an unreacted acid functionalgroup-containing monomer has been removed may be used as the base resin.

In the acid-modified polyolefin resin, the proportion of a part derivedfrom an unmodified polyolefin resin or olefin monomer is preferably 50parts by mass or more based on 100 parts by mass of a total amount ofthe acid-modified polyolefin resin.

A melting point of the acid-modified polyolefin resin is preferably 50°C. to 100° C. This melting point is preferably 60° C. to 98° C., morepreferably 70° C. to 98° C., and further preferably 75° C. to 95° C.From the viewpoint of solubility in a solvent and aging afterlamination, a low melting point is preferred, and from the viewpoint ofheat resistance and durability, a high melting point is preferred.

A molecular weight of the acid-modified polyolefin resin is notparticularly limited, but is, for example, 10,000 to 800,000, preferably50,000 to 650,000, more preferably 80,000 to 550,000, and furtherpreferably 100,000 to 450,000.

Then, the crosslinking agent of the first adhesive layer 11 will beillustrated. Examples of an epoxy-based compound to be the crosslinkingagent include a bisphenol A-type epoxy resin, a bisphenol F-type epoxyresin, a phenol novolak-type epoxy resin, a glycidyl ether-type epoxyresin, a glycidyl amine-type epoxy resin, and the like. A phenoxy resinis generally used as a polyhydroxypolyether resin, but when a phenoxyresin has an epoxy group derived from a raw material, it can be used asan epoxy-based compound of the crosslinking agent.

A bisphenol-type epoxy resin such as a bisphenol A-type epoxy resin or abisphenol F-type epoxy resin is a compound in which a basic structure isa bisphenol compound and an epoxy group has been introduced into a partof the structure. Since the bisphenol compound has two phenolic hydroxygroups, the bisphenol-type epoxy resin usually becomes a bifunctionalepoxy resin having a bisphenol skeleton.

In the present specification, the phenol novolak-type epoxy resin is acompound in which a basic structure is a phenol novolak resin and anepoxy group has been introduced into a part of the structure. The phenolnovolak resin is generally also referred to as “novolak” simply and isobtained by condensing a phenol compound and formaldehyde. An amount ofan epoxy group introduced per one molecule in the phenol novolak-typeepoxy resin is not particularly limited. Since a number of epoxy groupsare introduced into phenolic hydroxy groups which exist at a largenumber in the phenol novolak resin by reacting an epoxy group rawmaterial such as epichlorohydrin and the phenol novolak resin, thephenol novolak-type epoxy resin usually becomes a polyfunctional epoxyresin.

The phenol compound constituting the phenol novolak resin may be acompound having a phenolic hydroxy group, and a compound having noactive hydrogen other than a hydroxy group is preferred. Specificexamples of the phenol compound include monophenol compounds such asphenol (hydroxybenzene), cresol, and naphthol; bisphenol compounds suchas bisphenol A, bisphenol E, and bisphenol F; and the like. The phenolnovolak resin and the phenol novolak-type epoxy resin which include thebisphenol compound have a bisphenol skeleton.

One example of the phenol novolak-type epoxy resin having a bisphenolskeleton is shown in the formula (1).

In the formula (1), R¹ to R⁶ each are independently a hydrogen atom oran organic group such as a methyl group, and n is an integer of 0 to 10.R^(X)s are groups having an epoxy group. R^(X)s may be the same ordifferent, respectively. When n is an integer of 2 or more, R³ and R⁴may be the same or different, respectively.

Examples of the organic group when R¹ to R⁶ are not a hydrogen atominclude hydrocarbon groups such as a methyl group, an ethyl group, and aphenyl group, and halogen-substituted hydrocarbon groups such as atrifluoromethyl group. Inter alia, a methyl group is preferred.

Examples of the group having an epoxy group represented by R^(X) includean aliphatic group having an epoxy group, an alicyclic group having anepoxy group, an aromatic group having an epoxy group, and the like.Inter alia, a glycidyl group (another name 2,3-epoxypropyl group) ispreferred.

As the epoxy-based compound to be the crosslinking agent, the phenolnovolak-type epoxy resin having the bisphenol skeleton is preferred, andthe phenol novolak-type epoxy resin having a bisphenol A skeleton isparticularly preferred.

For example, in the resin represented by the formula (1) becomes a resinhaving a bisphenol A skeleton by satisfying at least one selected from(i) both of R¹ and R² are methyl groups, (ii) both of at least one setof R³ and R⁴ binding to the same carbon atom are methyl groups, and(iii) both of R⁵ and R⁶ are methyl groups.

An epoxy equivalent of the epoxy-based compound is preferably 100 to 300and more preferably 200 to 300. The epoxy equivalent (g/eq) correspondsto a molecular weight of the epoxy-based compound per one epoxy group,and it means that as this value is smaller, the number of epoxy groupsin the epoxy-based compound is larger. By using the epoxy-based compoundhaving a relatively small epoxy equivalent as the crosslinking agent,adhesiveness between the first adhesive layer 11 and the first adherend21 becomes good, and the acid-modified polyolefin resin of the baseresin is sufficiently crosslinked even when an addition amount of theepoxy-based compound is relatively small.

As specific examples of the phenol novolak-type epoxy resin, commercialproducts such as jER (registered trademark) 154, jER (registeredtrademark) 157S70, and jER (registered trademark) 157S65 manufactured byMitsubishi Chemical Corporation; EPICLON (registered trademark) N-730A,EPICLON (registered trademark) N-740, EPICLON (registered trademark)N-770, and EPICLON (registered trademark) N-775 manufactured by DICCORPORATION (all of the above are product names); and the like can alsobe used.

It is conceivable that in the first adhesive layer 11, it is possible toexert excellent adhesiveness to various adherends such as metals,glasses, and plastics, when both of an acid functional group of the baseresin and an epoxy group of the crosslinking agent function as anadhesive functional group to the first adherend. It is conceivable thatthe strength of the resin is reinforced and good durability togetherwith excellent adhesiveness is obtained, when a part of an acidfunctional group of the base resin and a part of an epoxy group of thecrosslinking agent are reacted to form a crosslinked structure of thebase resin and the crosslinking agent.

A crosslinking reaction between a part of an acid functional group ofthe base resin and a part of an epoxy group of the crosslinking agentmay progress during any one or more steps of: a step of forming thefirst adhesive layer 11; a step of laminating the first adhesive layer11 and the second adhesive layer 12; a step of laminating the firstadhesive layer 11 and the first adherend 21; a step of aging afterlamination of an adherend; and the like.

An adhesive composition constituting the first adhesive layer 11 canappropriately contain a miscible additive, an additional resin, aplasticizer, a stabilizer, a coloring agent, and the like as desired inaddition to the adhesive resin composed of the base resin and thecrosslinking agent.

The ratio of 0.01 to 30 parts by mass of the crosslinking agent to 70 to99.99 parts by mass of the base resin is preferable, letting a totalamount of adhesive resin components in the first adhesive layer 11 to be100 parts by mass. The ratio of 0.1 to 20 parts by mass of thecrosslinking agent to 80 to 99.9 parts by mass of the base resin is morepreferable.

If the ratio of the crosslinking agent is too large, it may be difficultto set the appropriate adhesion condition. If the crosslinking agent isnot contained, adhesiveness to the first adherend 21 becomesdeteriorated.

Examples of a method of forming the first adhesive layer 11 include amethod of producing a coating liquid including the base resin and thecrosslinking agent, coating the coating liquid on a substrate film, anddrying the coating liquid. Thereby, it becomes possible to form thefirst adhesive layer 11 as a thinner layer, and it is possible to reducethe first adhesive layer 11 and a laminate including the first adhesivelayer 11 in thickness.

A film thickness of the first adhesive layer 11 after drying correspondsto a film thickness of the first adhesive layer 11 in the adhesive resinlaminate 10. Examples of the film thickness of the first adhesive layer11 include 0.1 to 50 μm. The film thickness is preferably 0.5 to 10 μmand more preferably 0.7 to 5 μm. When the film thickness of the firstadhesive layer 11 is too large, workability on lamination with anadherend may be reduced.

As the coating liquid, a coating liquid which is obtained by dissolvingthe base resin and the crosslinking agent in a solvent is preferred. Asthe solvent, an organic solvent excellent in drying property aftercoating in addition to solubility of the base resin and the crosslinkingagent is preferred. A boiling point of the solvent is preferably, forexample, 150° C. or lower. Specific examples of the solvent include oneor two or more of aromatic solvents such as toluene, xylene, anisole,ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether,phenetol, butyl phenyl ether, ethylbenzene, diethylbenzene,pentylbenzene, isopropylbenzene, cymene, and mesitylene; aliphaticsolvents such as n-hexane; ketone-based solvents such as acetone, methylethyl ketone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentylketone, and 2-heptanone; ester-based solvents such as methyl lactate,ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methylpyruvate, ethyl pyruvate, methyl methoxypropionate, and ethylethoxypropionate; alcohol-based solvents such as methanol, ethanol,isopropyl alcohol, ethylene glycol, diethylene glycol, propylene glycol,and dipropylene glycol; and the like.

As the solvent used in the coating liquid, one may be used alone, or amixed solvent as a combination of two or more thereof may be used. Inthe case of the mixed solvent, it is also preferable to use an organicsolvent which dissolves the base resin well, together with an organicsolvent which dissolves the crosslinking agent well in combination. Assuch a combination, a combination of toluene which dissolves the baseresin well and methyl ethyl ketone which dissolves the crosslinkingagent well is preferred. In a method of producing the coating liquidincluding the mixed solvent, the base resin and the crosslinking agentmay be dissolved in the mixed solvent, or a solution of the base resinand a solution of the crosslinking agent may be mixed.

The mixing ratio in the mixed solvent is not particularly limited, butfor example, when toluene and methyl ethyl ketone are combined, themixing ratio is preferably in a mass ratio of 60 to 95:5 to 40 and morepreferably 70 to 90:10 to 30.

Then, the second adhesive layer 12 will be illustrated. The secondadhesive layer 12 is a layer composed of a polyolefin-based resin. Thesecond adhesive layer 12 may be of a monolayer structure, or may be of amultilayer structure. Examples of the multilayer structure include alaminate of a plurality of polyolefin-based resin layers.

Examples of the polyolefin-based resin constituting the second adhesivelayer 12 include one or two or more of polyethylene, polypropylene,poly-1-butene, polyisobutylene, a copolymer of ethylene and propylene, acopolymer of propylene and 1-butene, a random copolymer of propylene andethylene or α-olefin, a block copolymer of propylene and ethylene orα-olefin, and the like. Inter alia, polypropylene-based resins such ashomopolypropylene which is a homopolymer of propylene (hereinafter, maybe referred to as “homopolypropylene”), a block copolymer ofpropylene-ethylene (hereinafter, may be referred to as “blockpolypropylene”), and a random copolymer of propylene-ethylene(hereinafter, may be referred to as “random polypropylene”) arepreferred.

It is preferable that the second adhesive layer 12 includes a layercomposed of block polypropylene, due to excellent mechanical strength.

It is preferable that the second adhesive layer 12 has a supportproperty. For example, when the second adhesive layer 12 single body canbe conveyed as a base film or the like with a coating apparatus, alamination apparatus or the like, the second adhesive layer 12 has asupport property.

It is preferable that the second adhesive layer 12 includes a layercomposed of random polypropylene on a surface being in contact with thefirst adhesive layer 11, due to excellent adhesiveness with the firstadhesive layer 11.

Examples of a film thickness of the second adhesive layer 12 include 1to 200 μm. The film thickness is preferably 5 to 100 μm and morepreferably 10 to 50 μm. It is preferable that the film thickness of thesecond adhesive layer 12 is five times or more of the film thickness ofthe first adhesive layer 11. By reducing the first adhesive layer 11 inthickness, interlayer peeling to the first adherend 21 can besuppressed. By increasing the second adhesive layer 12 in thickness, thesupport property of the second adhesive layer 12 can be improved.

In the adhesive resin laminate 10 of the present embodiment, the firstadhesive layer 11 has a viscoelastic modulus measurement value E (150)at 150° C. of preferably 1.0×10⁴ Pa or more and 1.0×10⁸ Pa or less. Achart of a storage elastic modulus E′ of the first adhesive layer 11preferably shows a chart from a glassy state in a low temperature regionto an equilibrium region where a measurement value E′ becomes anapproximately equilibrium value via a transition region where themeasurement value E′ gradually reduces, with a temperature rise.Thereby, a temperature at which the first adhesive layer 11 adheres tothe first adherend 21 is apt to be low. As a result, it becomes easy tosequentially perform a step of adhering the second adhesive layer 12 tothe second adherend 22 after the first adhesive layer 11 has adhered tothe first adherend 21. The value E (150) can be adjusted by amodification amount of the modified polyolefin resin of the base resinin the resin composition constituting the first adhesive layer 11 and anaddition amount of the crosslinking agent.

The viscoelastic modulus measurement value E (150) of the first adhesivelayer 11 can be evaluated, for example, by measuring the storage elasticmodulus at 150° C. using a publicly known dynamic viscoelasticitymeasuring apparatus. As the dynamic viscoelasticity measuring apparatus,a dynamic viscoelasticity measuring apparatus “RSA-3” (product name) ofTA Instruments or the like can be used. A vibration frequency when thestorage elastic modulus is measured is, for example, 1 Hz.

Examples of a method of producing the adhesive resin laminate 10 includea method comprising: (1) a step of dissolving a modified polyolefinresin and an epoxy-based compound in a solvent to produce a coatingliquid; (2) a step of coating the coating liquid on a substrate film anddrying the coating liquid to produce the first adhesive layer 11; (3) astep of obtaining the second adhesive layer 12 having a film shape byextrusion molding; (4) a step of laminating the first adhesive layer 11on the substrate film, and the second adhesive layer 12; and (5) a stepof peeling the substrate film to obtain the adhesive resin laminate 10;in this order.

The coating of the coating liquid is as described above. The substratefilm is not particularly limited, but examples thereof include resinfilms poor in adhesiveness such as a film of a polyester resin such aspolyethylene terephthalate (PET) or polyethylene naphthalate (PEN); anda fluorine resin film A substrate film which has been subjected torelease treatment may be used. Examples of a releasing agent include asilicone-based releasing agent, a fluorine-based releasing agent, a longchain alkyl-based releasing agent, and the like.

Examples of a method of adhering the adhesive resin laminate 10 to thefirst adherend 21 and the second adherend 22 include a method including(1) a first step of laminating the first adherend 21 and the firstadhesive layer 11, and heat-pressing them to laminate the first adherend21 and the adhesive resin laminate 10, and (2) a step of laminating thesecond adherend 22 and the second adhesive layer 12, and heat-pressingthem at a temperature higher than a temperature of the first step by 30°C. or higher to laminate the second adherend 22 and the adhesive resinlaminate 10, in this order.

Thereby, a laminate is obtained in which the adhesive resin laminate 10and two adherends 21 and 22 are laminated in an order of the firstadherend 21, the first adhesive layer 11 and the second adhesive layer12 of the adhesive resin laminate 10, and the second adherend 22.

Examples of a material constituting the first adherend 21 include metalssuch as aluminum, copper, lead, zinc, iron, nickel, titanium, chromium,stainless, and alloy. Due to easy formation of a laminate with theadhesive resin laminate 10, it is preferable that the first adherend 21is a metal foil. A thickness of the metal foil is preferably 100 μm orless, more preferably 5 to 40 μm, further preferably 10 to 30 μm, andparticularly preferably 10 to 20 μm.

Examples of a material constituting the second adherend 22 includesynthetic resins composed of polyolefin resins such as orientedpolypropylene (OPP); polyamide resins such as nylon (Ny); polyesterresins such as polyethylene terephthalate (PET), polyethylenenaphthalate (PEN), and polybutylene terephthalate (PBT); polyether etherketone (PEEK), polyphenylene sulfide (PPS), and the like. Due to easyformation of a laminate with the adhesive resin laminate 10, the secondadherend 22 is preferably a synthetic resin film A thickness of thesynthetic resin film is, for example, 1 to 50 μm. The synthetic resinfilm may be of a monolayer structure, or of a multilayer structure.

As mentioned above, the present invention has been illustrated based ona preferred embodiment, but the present invention is not limited to theabove-mentioned embodiment, and various alterations can be made in arange not departing from the subject matter of the present invention.

By preparing two adhesive resin laminates 10 and laminating them so thatthe second adhesive layer 12 is arranged inward, a laminate includingthe first adhesive layer 11, the second adhesive layer 12, the secondadhesive layer 12, and the first adhesive layer 11 in this order may beformed. In this case, adhesiveness of both surfaces is high because ofthe first adhesive layer 11, and adhesiveness between respective layersalso becomes good.

Examples

The present invention will be specifically illustrated below by way ofExamples, but the present invention is not limited by Examples.

According to a constitution shown in Table 1, the first adhesive layer11 was produced. Specifically, a solution of a maleic acidanhydride-modified polypropylene-based resin and a phenol novolak-typeepoxy resin in toluene was coated with a bar coater on a PET substratefilm which had been subjected to release treatment, and the coatingsolution was dried.

TABLE 1 Base resin Crosslinking agent Addition Addition First adhesivelayer amount amount Film E (parts by (part(s) thickness (150) Materialmass) Material by mass) (μm) (Pa) Adhesive layer 1-1 Base resin A 90Crosslinking agent A 1 2.0 6.0E+05 Adhesive layer 1-2 Base resin A 95Crosslinking agent A 5 2.0 5.0E+05 Adhesive layer 1-3 Base resin A 80Crosslinking agent A 20 2.0 1.2E+07 Adhesive layer 1-4 Base resin A 60Crosslinking agent A 40 2.0 1.5E+07 Adhesive layer 1-5 Base resin A 95Crosslinking agent B 5 2.0 3.0E+05 Adhesive layer 1-6 Base resin A 95Crosslinking agent C 5 2.0 7.0E+05 Adhesive layer 1-7 Base resin A 100None 0 2.0 <1.0E+04  Adhesive layer 1-8 Base resin A 90 Phenoxy resin 102.0 <1.0E+04  Adhesive layer 1-9 Base resin B 90 Crosslinking agent A 102.0 4.0E+05 Adhesive layer 1-10 Base resin A 95 Crosslinking agent A 510.0 5.2E+05

In Table 1, the “base resin A” represents a maleic acidanhydride-modified propylene-1-butene copolymer. The “base resin B”represents maleic acid anhydride-modified polypropylene.

The “crosslinking agent A”, the “crosslinking agent B”, and the“crosslinking agent C” represent different kinds of phenol novolak-typeepoxy resins, respectively. Specifically, a bisphenol A-type compound inwhich all of R¹ to R⁶ are methyl groups in the above-mentioned formula(1) is the “crosslinking agent A”. A bisphenol E-type compound in whichR¹, R³, and R⁵ are methyl groups, and R², R⁴, and R⁶ are hydrogen atomsis the “crosslinking agent B”. A bisphenol F-type compound in which allof R¹ to R⁶ are hydrogen atoms is the “crosslinking agent C”.

The “phenoxy resin” is one kind of an epoxy-based compound which has abisphenol skeleton, but is not a novolak-type.

The value E (150) was expressed, for example, so that “1.0×10⁴”represents “1.0E+04”. The measurement results of the storage elasticmodulus E′ (Pa) of the adhesive layer 1-1, the adhesive layer 1-2, theadhesive layer 1-7, and the adhesive layer 1-8 are exemplified in thegraph of FIG. 2. A value E′ at 150° C. corresponds to E (150).

According to a constitution shown in Table 2, the second adhesive layer12 was produced by extrusion film formation or multilayer extrusion filmformation.

TABLE 2 First layer Second layer Third layer Second adhesive layerMelting Film Melting Film Melting Film Film point thickness pointthickness point thickness thickness T2 Material (° C.) (μm) Material (°C.) (μm) Material (° C.) (μm) (μm) (° C.) Adhesive layer 2-1 r-PP 130 10b-PP 150 20 r-PP 130 10 40 130 Adhesive layer 2-2 r-PP 130 40 None None40 130 Adhesive layer 2-3 b-PP 150 40 None None 40 150

In Table 2, “r-PP” represents random polypropylene and “b-PP” representsblock polypropylene. When the second adhesive layer 12 is constituted ofa multilayer structure, a side being in contact with the second adherend22 is set as a “first layer”, and a “second layer” and a “third layer”are set in order in the first adhesive layer 11 side.

Then, after lamination of the first adhesive layer 11 on a PET substratefilm which had been subjected to release treatment and the secondadhesive layer 12 according to a combination shown in Table 3, the PETsubstrate film which had been subjected to release treatment was peeledto obtain the adhesive resin laminate 10.

TABLE 3 E Adhesiveness Adhesiveness Sequential stable (150) with firstwith second production Comprehensive First adhesive layer Secondadhesive layer (Pa) adherend adherend property evaluation Example 1Adhesive layer 1-1 Adhesive layer 2-1 6.0E+05 ⊙ ◯ ◯ ⊙ Example 2 Adhesivelayer 1-2 Adhesive layer 2-1 5.0E+05 ⊙ ◯ ◯ ⊙ Example 3 Adhesive layer1-3 Adhesive layer 2-1 1.2E+07 ◯ ◯ ◯ ◯ Example 4 Adhesive layer 1-4Adhesive layer 2-1 1.5E+07 Δ ◯ ◯ Δ Example 5 Adhesive layer 1-5 Adhesivelayer 2-1 3.0E+05 ⊙ ◯ ◯ ⊙ Example 6 Adhesive layer 1-6 Adhesive layer2-1 7.0E+05 ⊙ ◯ ◯ ⊙ Comparative Adhesive layer 1-7 Adhesive layer 2-1<1.0E+04  X ◯ X X Example 1 Comparative Adhesive layer 1-8 Adhesivelayer 2-1 <1.0E+04  X ◯ X X Example 2 Example 7 Adhesive layer 1-9Adhesive layer 2-1 4.0E+05 ◯ ◯ ◯ ◯ Example 8 Adhesive layer 1-10Adhesive layer 2-1 5.2E+05 ◯ ◯ Δ Δ Example 9 Adhesive layer 1-3 Adhesivelayer 2-2 1.2E+07 ◯ Δ ◯ Δ Example 10 Adhesive layer 1-3 Adhesive layer2-3 1.2E+07 ◯ ◯ ◯ ◯ Comparative Adhesive layer 1-3 None 1.2E+07 ◯ ◯ X XExample 3 Comparative None Adhesive layer 2-1 None X ◯ X X Example 4

The first adhesive layer 11 of the adhesive resin laminate 10 and aplate of aluminum as the first adherend 21 were overlapped and stuckwhile a pressure of 0.25 MPa and heat at 100° C. were applied. Then, thesecond adhesive layer 12 on a surface on an opposite side of theadhesive resin laminate and a PET film as the second adherend 22 whichhad not been subjected to release treatment were overlapped, and apressure of 0.25 MPa and heat at 160° C. were applied to stick them, andthereby, a laminate in which the first adhesive layer 11 and the firstadherend 21, and then the second adhesive layer 12 and the secondadherend 22 were stuck in this order was produced.

The sequential stable production property was evaluated at n=5 byrepeating five times the work of sticking the first adhesive layer 11and the first adherend 21, and the second adhesive layer 12 and thesecond adherend 22 in this order, respectively. For evaluation criteria,the case where the work could be performed without a problem all fivetimes was evaluated as “◯”, the case where a fish eye was generated inone time to two times of the work was evaluated as “Δ”, and the casewhere a fish eye was generated three or more times was evaluated as “x”.

After aging was performed at 60° C. for 5 days after production of theabove-mentioned laminate, the adhesiveness of the adhesive resinlaminate 10 was measured using a sample which was obtained by cuttingthe resulting laminate into a width of 15 mm. The average adhesivestrength (N/15 mm) at the time when each sample was peeled by T-shapepeeling at a speed of 50 mm/min under an environment of a temperature of90° C. was measured. The case where the average adhesive strength was 10N/15 mm or more was evaluated as “0”, the case where the averageadhesive strength was 5 N/15 mm or more and less than 10 N/15 mm wasevaluated as “◯”, the case where the average adhesive strength was 2N/15 mm or more and less than 5 N/15 mm was evaluated as “Δ”, and thecase where the average adhesive strength was less than 2 N/15 mm wasevaluated as “x”.

The comprehensive evaluation was performed based on evaluation of 3items including the workability of the adhesive resin laminate 10, theadhesiveness with the first adherend 21, and the adhesiveness with thesecond adherend 22.

The comprehensive evaluation in the case where one or more itemsincluded “0” and other items also included “◯” was evaluated as “⊙”.

The comprehensive evaluation in the case where all of 3 items included“◯” was evaluated as “◯”.

The comprehensive evaluation in the case where 2 items included “◯” andone item included “Δ” was evaluated as “Δ”.

The comprehensive evaluation in the case where even one item included“x” was evaluated as “x”.

Each of the adhesive resin laminates 10 of Examples 1 to 10 had acomprehensive evaluation of “⊙”, “◯” or “Δ”. With regard to Exampleseach having a comprehensive evaluation of “0” or “A”, it is conceivablethat such an evaluation is given because E (150) is slightly large inExamples 3 and 4, because a resin of the base resin is different fromthat of other Examples in Example 7, because a film thickness of thefirst adhesive layer 11 is slightly large in Example 8, and because thecrosslinking agent is different from that of other Examples in Examples9 and 10.

Additionally, the comprehensive evaluations of Comparative Examples 1and 2 in each of which the first adhesive layer 11 had a viscoelasticmodulus measurement value E (150) of less than 1.0×10⁴ Pa were evaluatedas “x”.

In Comparative Example 1, the crosslinking agent is not used in thefirst adhesive layer 11.

The comprehensive evaluation of Comparative Example 3 in which theadhesive resin laminate 10 was composed only of the first adhesive layer11 was evaluated as “x”.

The comprehensive evaluation of Comparative Example 4 in which theadhesive resin laminate 10 was composed only of the second adhesivelayer 12 was evaluated as “x”.

DESCRIPTION OF THE REFERENCE NUMERALS

-   10: Adhesive resin laminate-   11: First adhesive layer-   12: Second adhesive layer-   21: First adherend-   22: Second adherend

What is claimed is:
 1. A method of producing an adhesive resin laminatehaving at least a first adhesive layer and a second adhesive layer,wherein said first adhesive layer comprises a base resin and acrosslinking agent, said base resin is a modified polyolefin resin andsaid crosslinking agent is an epoxy-based compound, said second adhesivelayer comprises a polyolefin-based resin, and said first adhesive layerhas a viscoelastic modulus measurement value E (150) at 150° C. of1.0×10⁴ Pa or more and 1.0×10⁸ Pa or less, the method comprising: (1) astep of dissolving said modified polyolefin resin and said epoxy-basedcompound in a solvent to produce a coating liquid; (2) a step of coatingsaid coating liquid on a substrate film and drying the coating liquid toproduce said first adhesive layer; (3) a step of obtaining said secondadhesive layer having a film shape by extrusion molding; (4) a step oflaminating said first adhesive layer on said substrate film and saidsecond adhesive layer; and (5) a step of peeling said substrate film toobtain said adhesive resin laminate, in this order.
 2. A method ofproducing a laminate comprising an adhesive resin laminate having atleast a first adhesive layer and a second adhesive layer; and first andsecond adherends, said adhesive resin laminate and said first and secondadherends being laminated in an order of the first adherend, said firstadhesive layer of said adhesive resin laminate, said second adhesivelayer of said adhesive resin laminate, and the second adherend, whereinsaid first adhesive layer comprises a base resin and a crosslinkingagent, said base resin is a modified polyolefin resin and saidcrosslinking agent is an epoxy-based compound, said second adhesivelayer comprises a polyolefin-based resin, and said first adhesive layerhas a viscoelastic modulus measurement value E (150) at 150° C. of1.0×10⁴ Pa or more and 1.0×10⁸ Pa or less, the method comprising: (1) afirst step of laminating said first adherend and said first adhesivelayer and heat-pressing said first adherend and said first adhesivelayer to laminate said first adherend and said adhesive resin laminate;and (2) a step of laminating said second adherend and said secondadhesive layer and heat-pressing said second adherend and said secondadhesive layer at a temperature higher than a temperature in said firststep by 30° C. or more to laminate said second adherend and saidadhesive resin laminate, in this order.